Conjoint polymerization product of dicarboxylic compounds and vinylic compounds



Patented July 29, 1947 CONJOINT POLYMERIZATION PRODUGT OF DICARBOXYLIC COMPOUNDS AND VI NYLIC COMPOUNDS Howard L. Gerhart, Milwaukee, Wis, assignor to Pittsburgh Plate Glass Company, Allegheny County, l a.,a corporation of Pennsylvania No Drawing. Original application August 1.5,

1941', Serial No. 407,010, now Patent No. 2,392,139, dated January 1, 1946. Divided and this application March 30, 1944, Serial No.

2 Claims.

The present invention relates to artificial resins and it has particular relation to such resins as are obtained by reacting substituted or unsubstituted ethylene afi dicarboxylic acids or anhydrides thereof with a polymerizable olefin,

One object of the invention is to provide a clear, hard, tough, stable and well plasticized resin of the above type which is relatively free from bubbles or cavities.

A second object of the invention is to provide a resinifying fluid materialthat can be cast, or can be employed as an investment median and formed into clear, hard, durable and tough bodies at low temperatures and with but little distortion.

These and other objects will be apparent from consideration of the following specification and the appended claims.

It has heretofore been proposed to heat an unsaturated dicarboxylic acid, such as maleic' acid or its anhydride and a polymerizable olefin such as styrene to obtain polymerization products of white powdery character, which are soluble in acetone and dilute alkalies. 1

My copending application Serial No. 242,127, filed November 23, 1938, now issued as Patent No. 2,297,351 as of the date of Sept, 29, 1942, is based upon the discovery that unsaturated dicarboxylic acids of the type of maleic acid, or maleic an ydride, or fumaric acid,- or substituted maleic or fumaric acid andpolymerizable oleflns of the type of styrene will under the influence of actinic radiation react to form clear and hard resins which are relatively insoluble and substantially .free of voids. These resins are well adapted for .molding, cuttin pressing, or otherwiseforming into bodies of great beauty. The resinforming reaction may be carried out completely or at least in its final stages by casting the reacting 1 mass in a suitable mold, thus obtaining directly the finally desired object.

However, considerable difficulty has been experienced in adequate plasticization of the resin in order to obtain clear, hard and tough bodies, that maintain that condition over long periods of time. Very few plasticizers are adequately compatible to admit of satisfactory use and those that are compatible usually are too volatile to admit of permanent plasticization.

The present invention is based upon the dis- I covery that carbonyl compounds which'include within their structure the group z I are quite generally of particular value as plasticizers for resins of the above-described type. The plasticizers may be either or open, chain or cyclic character, the type formulae of which are:

CHa(]3R and Ur ewhere R and)! are organic radicals. Examples of the first-mentioned class of compounds include:

Diacetone alcohol CHa(|I|)-CH2C OH O CH:

Acetophenone Derivatives of acetophenone containing groups such as methyl, nitro, amino and the like in meta and para or even ortho positions are contemplated.

Mesityl oxide C Ha omc cn=c 30, ll

methyl and ethyl acetone, methyl ethyl ketone, I etc., areusefulr Carbonyl compounds represented by the generic cyclic formula include:

' Isophorone Camphor v Cyclohexanone Ortho 'andpara methyl cyclohexanone seems to be satisfactory. v The reaction to form the new compositions is typified by that between maleic acid or maleic acid anhydride and styrene. vThe two combetween the two f-carboxyl groups.

'. coumaro'ne and the like.

pounds, along with an appropriate plasticizer are simply admixed directlyor are introduced intoa solvent, such as triacetin and are then caused to'react by actinic irradiation at a temperature within the range or about 20 to 50 0. Irradiation of the reactants may be continued 4 resins in great variety. The ratio of the dicarboxylic acid to the olefinic compound is susceptibleof wide variation,-'but' for purposes of throughout the period of reaction, but it may be discontinued after the reaction hasistarted; It. is also possible to introduce a small amount (e. g. 1 to of preliminarily irradiated reactants into the main batch further irradiation. f v

Reaction may also be initiated by application of heat and after it has progressed'sumciently, far, heating is discontinued. Iii very hard products are desired the mass may be finally heat treated at a suitable temperature (e. g. 100-200 C.) until the desired stage is reached. The reaction can be brought .to completion within an hour or less, but byreducing the degree or time or irradiation it is possible to extend it over a 1 period of several days.

- 1 The. reaction product obtained from maleic anhydride and styrene may be represented by the formula:

-gHcncm-orrr m ii where a: represents the number of the foregoing illustration may be considered as approximately molar.

oxidizing agents such as benzoyl peroxide may be employedto speed up reaction of the resinforming materials. Reducing agents, such as hydroquinone'pyrogallol, tannic acid, etc., may

and thus toobviate andthen to press them to shape. v

'A further application of the invention consists in providing a layer'of polymerizable materials be employed to retard reaction.

As previously. stated, the resinous bodies are insoluble, butit is possible to cast incipiently polymerized masses into molds'in which hardening to final form is effected. Polymerization in molds formed of soft glass, Pyrex, or other material and plasticizer betweentwo sheets of glass. By irradiating this glass; it is possible to form a film or transparent closely adherent resin between the glass sheets, thus forming a safety glass. The materials may be partially polymerized prior to application to glass. In a similar manner this class of resins may be employed in theilamination of wood. fabrics or other materials."

groups in the molecule and is oi variable value.

, Since the reaction is general in character and applies to many unsaturated dicarboxylic acids or anhydrides; i. e., substituted maleic or fumaric acid and to many of the polymerizable oleflns, the product may be represented by the type formula:

amples of possible ethylene as dicarboxylic acids or ethylenic dicarboxylic acids which are transtormable to 0.5 form, which may be employed,

include maleic acid (above described), iumaric acid, the mono or di chloro substituted maleic and fumaric acids, alkylated maleic and fumaric acids, such as itaconic, citraconic acid, mesa-conic acid, mono. and di phenyl maleic acid, benzyl maleic, dibenzyl maleic, ethyl maleic, or any similar acids containing a double bond in the chain 'The number of polymerizable pounds is als'overy large andof general'character. It includes styrene above described, vinyl acetate, vinyl chloride, methyligsty'rene, parahydroxy styreneacrylic acid, methyl, ethyl, or other esters of jacryli acid, acrolein',- unsaturated ketones 'lsuch as methyl. vinyl ketone, indene,

Styrene, methyl styrene, indene and coumarone constitute polymerizable aralkene hydrocarbons. It is to be understood that any one or more of I the dicarboxylicfacids can be combined with any one or more of the ol'efinic compounds, to provide Resinous bodies can be cut to any desired'form and then polished to provides. great variety of articles. The resins and scraps of the resin under heat and pressure, or the comminuted material may be mixed with further polymerizable material whichbyappropriate treatment will be converted into hard bonding resins. I Oilsoluble dyes, such as Rhodamin B, Victoria Green and pigmentssuoh as titanium dioxide may be in- .corporated into the resins prior to final solidification. a

The new resin may beemployed in the formation of optical lenses, jars, or lids for jars for cosmetics, drugs, foods and the like. They may be cast or cut to form an indefinite variety of handles, buttons, and'objects of similar nature, or cast about specimens or objects of art to effect an embedment thereof. They may also be used for the formation of panels and coverings for electrical apparatus'of a great variety.

Application of the principles of the invention is illustrated by the following example:

I Example I I Grams Maleic anhydride 25 Styrene 35 In the above example the mixture was preferably brought to a temperaturesufiicient to obtain mutual solution of thecomponents. Polymerization was then eifected by irradiation with actinic rays. The rate of polymerization wascontrolled by increase or decrease of the intensity "of irradiation and/orthe temperature. Itcan be brought But slight distortion takes place during polymerization. The resin is of exceptional clarity and is not subject to change of color upon aging.

All of these qualities combine to provide a resin par excellence for embedding specimens, such as insects, flowers and biological specimens. An object, such as a beetle can be introduced into a solution of styrene and maleic acid or anhydride containing a plasticizer in a container of suitable size and shape and the reaction to form the solid resin effected, at temperatures sufliciently low to obviate damage to the specimen, merely by mild irradiation. There is no damage to the specimen, due to shrinkage and distortion of the medium during setting. The reaction is. sufllciently rapid to be commercially feasible.

Example II A sample of a solution from Example I was placed between two-glass plates of soft glass and irradiated for one hour as described. The resin formed as a thin film between the plates which were not easily separated.

Example III A portion of the solution of Example I was irradiated for five minutes until it had congealed to incipient gellation (the mass could still be poured). This enabled more of the material to be placed between the plates. During the second minutes of irradiation, pressure was applied to the plates. The finished plates adhered well andflshattered with dimculty.

In the foregoing examples the dicarboxyllc acids and their anhydrides are to be considered as equivalents, since each anhydride is derived from the acid merely by elimination of a mole of water and the ester is the same regardless of 60 whether the acid or the anhydride is employed. Therefore, the term anhydride in the claims includes the acids and the term acid includes the anhydrides.

This is a division of my copending application Serial No. 407,010, filed August 15, 1941, now Patent No. 2,392,139 for Conjoint polymerization product of dicarboxylic compounds and vinylic compounds.

The application is also a companion of my application Serial No. 395,062, filed May 24, 1941, and entitled Plasticized styrene-maleic resin composition.

The embodiments of the invention herein described are merely exemplary and numerous modifications may be made therein without departure from the spirit of the invention or the scope or the appended claims.

What I claim is:

1. A method of preparing a hard, plasticized styrene-maleic anhydride body, which method I comprises placing a mixture of about 25 parts oi! maleic anhydride and 30 parts of styrene together with about 30 parts of a plasticizer from the class consisting of methyl levulinate, acetophenone, diacetone alcohol and mesityl oxide in a mold of desired configuration and polymerizing the styrene and maleic anhydride to form the resin as a body containing the plasticizer imbibed therein.

2. A method of preparing a hard, plasticized styrene-maleic anhydride body, which method comprises placing a mixture of about 25 parts of maleic anhydride, 30 parts of styrene and 10 to based upon the resin components of a plasticizer selected from the class consisting of methyl levulinate, acetophenone, diacetone alcohol and mesityl oxide in a mold of desired configuration and polymerizing the styrene and maleic anhydride to form the resin as a body containing the plasticizer imbibed therein.

HOWARD L. GERHART.

REFERENCES CITED The following references are of record in the file 01 this patent:

UNITED STATES PATENTS Number Name Date 2,321,897 Britton et al. June 15, 1943 2,047,398 Voss et al. July 14, 1936 2,252,091 Muller et al Aug. 12, 1941 2,058,794 Macht et al. Oct. 6, 1936 2,188,903 Kauppl et al. Feb. 6, 1940 2,327,007 Bent et al. Aug. 17, 1943 FOREIGN PATENTS Number Country Date 491,576 Great Britain 1938 

